1. Field of the Invention
The present invention relates to a golf ball, in particular a solid golf ball excellent in resilience and durability, and a manufacturing method thereof.
2. Description of the Background Art
Conventionally, the core of a golf ball has been manufactured by heating a rubber composition having a co-crosslinking agent such as metallic salt of unsaturated carboxylic acid and a crosslinking initiator such as organic peroxide blended into a rubber component chiefly including polybutadiene, to crosslink rubber molecule main chains. As the metallic salt of unsaturated carboxylic acid, zinc acrylic acid has generally been used. When the rubber composition is heated, the crosslinking initiator such as dicumyl peroxide dissociates to generate a free radical, which is considered to attack the rubber molecule main chain or the co-crosslinking agent to cause graft polymerization of the co-crosslinking agent to the main chain of the rubber molecule or the crosslinking between the main chains. The state of dispersion of the co-crosslinking agent such as metallic salt of unsaturated carboxylic acid within the rubber composition, and the speed of its crosslinking reaction to the main chain of the rubber molecule will considerably affect basic physical properties of the rubber composition after crosslinking, and will further affect properties of a golf ball with its solid core formed thereof.
Thus, in order to improve dispersibility of the co-crosslinking agent within the rubber composition, a technique to coat a particle surface of the zinc acrylic acid with higher fatty acid or metallic salt of higher fatty acid has conventionally been proposed (U.S. Pat. No. 4,561,657 and Japanese Patent Laying-Open No. 60-92781).
Further, a technique to use, as the co-crosslinking agent, metallic salt of unsaturated carboxylic acid having an average particle size of not greater than 5 xcexcm, or unsaturated carboxylate having particle size distribution of 0.1-5 xcexcm and an average particle size of 1-4.5 xcexcm has also been proposed to improve the dispersibility of the co-crosslinking agent within the rubber composition (Japanese Patent Laying-Open Nos. 8-196661, 9-235413, 11-57068, and U.S. Pat. No. 6,136,906).
These techniques are advantageous in that the dispersibility of the co-crosslinking agent within the rubber composition is improved and thus hardness of the rubber composition is increased. However, due to the co-crosslinking agent so finely dispersed, the density of crosslinking between the rubber molecule main chains, which is most likely to contribute to resilience, is decreased, whereas the graft polymerization of the co-crosslinking agent with the rubber molecule main chain, which is unlikely to contribute to the resilience, is increased, resulting in unsatisfactory resilience.
Proposed to improve such resilience is a technique to use an organic sulfur compound together with metallic salt of xcex1,xcex2-unsaturated carboxylic acid (Japanese Patent Laying-Open Nos. 2-297384, 9-122273, 10-244019, 2000-102627, and U.S. Pat. No. 5,252,652). With this technique, however, the added organic sulfur compound captures the free radical of the crosslinking initiator, thereby limiting the activity of the crosslinking initiator. Thus, compared to the case where no organic sulfur compound is being added, the time of reaction is lengthened and a blended amount of crosslinking initiator should be increased. The basic characteristics of the rubber composition may also be impaired.
An object of the present invention is to improve dispersibility of a co-crosslinking agent in a rubber composition for use in manufacturing a solid core of a golf ball, by micro-encapsulating the co-crosslinking agent. Another object of the present invention is to provide a golf ball improved in resilience and durability, by micro-encapsulating an organic sulfur compound together with a portion of the co-crosslinking agent to properly restrict the speed of graft polymerization of the co-crosslinking agent with a rubber molecule main chain and to give priority to crosslinking reaction between the rubber molecule main chains.
According to an aspect of the present invention, the golf ball includes a solid core, and a cover surrounding the solid core, wherein the solid core includes a rubber composition having a co-crosslinking agent blended therein, with a portion of the co-crosslinking agent being micro-encapsulated within a thermoplastic resin.
Here, preferably 70-99 wt. % of the entire co-crosslinking agent is micro-encapsulated. As the co-crosslinking agent, an xcex1,xcex2-unsaturated carboxylic acid and/or a metallic salt thereof is suitably employed. The thermoplastic resin preferably has a softening point in a range of 80-250xc2x0 C.
According to another aspect of the present invention, the golf ball includes a solid core and a cover surrounding the solid core, wherein the solid core is formed of a rubber composition that contains a portion of a co-crosslinking agent and an organic sulfur compound micro-encapsulated within a thermoplastic resin, and a remaining portion of the co-crosslinking agent not encapsulated. Here, the organic sulfur compound is preferably one of polysulfides, thiophenols and bivalent metallic salts of the thiophenols.
According to a further aspect of the present invention, the manufacturing method of a golf ball having a solid core and a cover surrounding the solid core includes:
(1) a step of blending a portion of a co-crosslinking agent in a non-encapsulated state and a remaining portion of the co-crosslinking agent and possibly an organic sulfur compound micro-encapsulated within a thermoplastic resin into a rubber composition, and
(2) a step of heating the rubber composition to a temperature higher than a softening point of the thermoplastic resin for crosslinking.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention.
The golf ball according to the present invention is formed with a solid core surrounded by a cover material. The cover material includes a thermoplastic resin such as ionomer resin or trans 1,4-polyisoprene (TPI). The rubber composition of the solid core contains a co-crosslinking agent, a portion of which is micro-encapsulated within a thermoplastic resin.
The co-crosslinking agent for use in the present invention may be xcex1,xcex2-unsaturated carboxylic acid having a carbon number of 3-8 and/or metallic salt thereof. Examples of the xcex1,xcex2-unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid and others. Among them, the acrylic acid is particularly suitable for the purpose of improving the resilience. Examples of the metallic salt include zinc salt, sodium salt, magnesium salt, calcium salt, aluminum salt and others. Among them, zinc salt is particularly preferable. Although zinc acrylic acid is suitably used as the co-crosslinking agent, two or more types selected from the foregoing can be used together.
In the present invention, it is preferable to encapsulate a portion of the co-crosslinking agent and an organic sulfur compound, where appropriate, within the thermoplastic resin. Herein, the organic sulfur compound is a concept including a metal-containing organic sulfur compound. As the organic sulfur compound, thiophenols such as pentachloro thiophenol, 4-t-butyl thiophenol and 2-benzamide thiophenol, thio carboxylic acids such as thio benzoic acid, and sulfides such as monosulfide, disulfide and polysulfide may be used. As the metal-containing organic sulfur compound, zinc salt, magnesium salt and sodium salt of thiophenols or thio carboxylic acids may be used. The monosulfide is, e.g., diphenyl monosulfide, and the disulfide is, e.g., diphenyl disulfide. The polysulfide is, e.g., diphenyl polysulfide, such as dibenzyl polysulfide, dibenzoyl polysulfide, dibenzothiazoyl polysulfide, or dithiobenzoyl polysulfide. As such sulfides, those having various types of substituent groups, such as methyl group, ethyl group, amino group, hydroxyl group and others, in the phenyl group included in the molecule may also be used.
The thermoplastic resin for use as a film material of the microcapsule has a softening point in a range of 80-250xc2x0 C., preferably in a range of 100-200xc2x0 C., and more preferably in a range of 120-160xc2x0 C. If the softening point is lower than 80xc2x0 C., the microcapsule may break during kneading of the rubber composition. If it exceeds 250xc2x0 C., however, the thermoplastic resin as the film material of the microcapsule may not melt at a temperature (hereinafter, xe2x80x9ccrosslinking temperaturexe2x80x9d) at which crosslinking of the rubber composition normally takes place, hindering release of the co-crosslinking agent and the organic sulfur compound from the microcapsule. Accordingly, the type of the thermoplastic resin is preferably determined taking into account a relation between its softening point and the crosslinking temperature of the rubber composition.
Examples of the thermoplastic resin for use as the film material of the microcapsule in the present invention are polystyrene, polyethylene, polypropylene, polyurethane, nylon resin, acrylic resin, methacrylic resin, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, vinyl chloride resin, butadiene resin, butene resin, polycarbonate, ABS resin, and AS resin. When chlorine resin such as the vinyl chloride resin is to be used, the one soluble in an organic solvent and having a softening point close to an intended temperature will be suitable.
As a method of micro-encapsulating the co-crosslinking agent alone or the co-crosslinking agent and the organic sulfur compound within the thermoplastic resin, any of the known methods for micro-encapsulation can be employed. One of such methods suitably used is an evaporation process in solvent. This process uses water or oil as a medium for encapsulation, in which a solution of a film material containing a core material is dispersed in the form of drops, and the solvent is eliminated to form a hard capsule film. Specifically, a solvent having a boiling point lower than that of water and a vapor pressure greater than that of water and not dissoluble with water is first selected, and a polymer of the film material is dissolved therein. In this solution, a water solution of the core material is dispersed to form a (W/O) type emulsion. Another water solution including protective colloid is prepared as the medium for encapsulation, to which the foregoing emulsion is dispersed while stirring, so that a [(W/O)/W] type complex emulsion is generated. In this system, drops of the water solution enveloped with the polymer solution are floating in the water. As the system undergoes processes of warming, decompression, solvent extraction and others, the solvent of the polymer is dried, and thus, a hard film of the polymer, or the microcapsule, is formed.
Another suitable method is an air-suspension technique. In this technique, a core material (powder) is fluidized by an airflow and suspended in the air, and an emulsion with a thermoplastic resin as the film material emulsified therein is sprayed onto the surface of the suspended powder. The air is then heated to vaporize the medium, so that the capsule film is formed. Yet another method suitably used is a spray dry method, wherein a core material is suspended in an emulsion with a thermoplastic resin as the film material emulsified therein, and the suspension is sprayed to form fine particles. The fine particles are instantaneously dried, and thus, the capsule film is formed. The encapsulation method used in the present invention is not limited to any specific one. Other methods, such as a method of encapsulating powder particles under a dry condition (by mixing particles of a core material and finer particles of a film material and applying impact by centrifugal force, for example, to fill the film material in the surface of the core material), may also be employed.
The microcapsule obtained in the above-described manner preferably contains 70-95 wt. % of the co-crosslinking agent. If it is less than 70 wt. %, release of the co-crosslinking agent will be insufficient. If it exceeds 95 wt. %, manufacture of homogeneous microcapsules will become difficult. The blended amount of the micro-encapsulated co-crosslinking agent in the rubber composition of the solid core, in terms of co-crosslinking agent, is 10-70 parts by weight and more preferably 15-40 parts by weight with respect to 100 parts by weight of the rubber component. If it is less than 10 parts by weight, crosslinking density of a sufficient level cannot be obtained. If it exceeds 70 parts by weight, in addition to an increase in hardness, graft polymerization of the co-crosslinking agent with the rubber molecule main chain will be promoted, which is disadvantageous from the standpoint of resilience.
The microcapsule preferably contains 0.3-10 wt. % of, and preferably 0.3-7 wt. % of, the organic sulfur compound. If it is less than 0.3 wt. %, the effect of blending the organic sulfur compound will be insufficient. If it exceeds 10 wt. %, physical properties of the rubber composition will be degraded. The blended amount of the micro-encapsulated organic sulfur compound to the rubber composition of the solid core, in terms of the organic sulfur compound, is preferably 0.05-5.0 parts by weight, more preferably 0.1-3.0 parts by weight, and still more preferably 0.3-1.5 parts by weight with respect to 100 parts by weight of the rubber component.
The Sxe2x80x94S bond or Cxe2x80x94S bond of the organic sulfur compound tends to dissociate when heated and generate free radicals, which would act on the rubber molecule main chain as well as the co-crosslinking agent, thereby affecting the crosslinking pattern. When the blended amount of the organic sulfur compound is less than 0.05 parts by weight, the effect of blending the same is not enjoyed. If it exceeds 5.0 parts by weight, the crosslinking density decreases. In this case, soft touch cannot be obtained, and resilience is also degraded.
If the organic sulfur compound is not encapsulated, the Sxe2x80x94S bond or Cxe2x80x94S bond thereof will dissociate when heated, to generate free radicals, as described above, which would capture free radicals of the crosslinking initiator to restrict the crosslinking reaction. Thus, according to the present invention, the organic sulfur compound is micro-encapsulated to restrict capturing of the free radicals of the crosslinking initiator, thereby efficiently promoting the crosslinking reaction between the rubber molecule main chains. Accordingly, it becomes unnecessary to conduct high-temperature crosslinking or to blend a large amount of crosslinking initiator in an effort to achieve the crosslinking reaction in a shorter period of time.
Further, it is known that blending of the organic sulfur compound into the rubber composition causes the rubber molecule main chain to make a transition from the cis structure to the trans structure. Such transition however can be restricted by micro-encapsulation. The rubber molecule main chain of the cis structure is superior in resilience to that of the trans structure. Thus, according to the present invention, the transition of the main chain to the trans structure is restricted by micro-encapsulating the organic sulfur compound, so that resilience greater than in the case of the rubber composition with a non-encapsulated organic sulfur compound blended therein is achieved.
While the resilience is increased using the microcapsules, durability is degraded as the crosslinking points between the rubber molecule main chains and the co-crosslinking agent comparatively decrease. Thus, according to the present invention, a small amount of non-encapsulated co-crosslinking agent is blended into the rubber composition to allow the graft polymerization of the rubber molecule main chain with the co-crosslinking agent to the extent that the resilience is unimpaired, to improve the durability.
In the present invention, the co-crosslinking agent micro-encapsulated within the thermoplastic resin that melts at the aforementioned specific temperature and the non-encapsulated co-crosslinking agent are employed at the same time. Using the micro-encapsulated co-crosslinking agent, the speed of the graft polymerization of the rubber molecule main chain and the co-crosslinking agent is controlled, so that the crosslinking density between the rubber molecule main chains can be optimized. This improves the resilience. Blending a small amount of the non-encapsulated co-crosslinking agent, the graft polymerization is allowed to the extent that the resilience is not degraded, as described above. This can improve the durability.
The micro-encapsulated co-crosslinking agent is 70-99 wt. % of, preferably 80-97 wt. % of, and more preferably 80-94 wt. % of the entire co-crosslinking agent. If it is less than 70 wt. %, the effect of improving the resilience by micro-encapsulation is small. If it exceeds 99 wt. %, improvement of the durability cannot be fully expected.
The rubber composition for the solid core contains, besides the co-crosslinking agent micro-encapsulated possibly with the organic sulfur compound and the co-crosslinking agent in the non-encapsulated state, a rubber component, an organic peroxide, a filler and others. As the rubber component, diene type rubber of either natural rubber or synthetic rubber may be used. In particular, high cis polybutadiene rubber having a cis-1, 4 bond content of preferably at least 40%, more preferably at least 70%, and still more preferably at least 90%, is preferred. To this high cis polybutadiene rubber, natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), ethylene-propylene-diene terpolymer (EPDM) or other types of diene type rubber may be blended where appropriate.
The organic peroxide is blended primarily as a crosslinking initiator to form crosslinks between the rubber molecule main chains. Since the crosslinking pattern by virtue of the organic peroxide primarily contributes to resilience, the blended amount of the organic peroxide is determined taking into consideration a desired property of the solid core. Examples of the organic peroxide include dicumyl peroxide, 1, 1-bis (t-butyl peroxy)-3,3,5-trimethyl cyclohexane, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, di-t-butyl peroxide and others. Among them, dicumyl peroxide is particularly preferable. The organic peroxide is blended 0.1-5.0 parts by weight, and more preferably 0.3-3.0 parts by weight, with respect to 100 parts by weight of the rubber component. If it is less than 0.1 parts by weight, the crosslinking density is low, so that hardness and resilience are insufficient. If it exceeds 5.0 parts by weight, however, the crosslinking density increases, and the hardness becomes too high.
Examples of the filler include metallic powders of high specific gravity, such as tungsten powder, molybdenum powder, and metallic salts of zinc oxide, barium sulfate and calcium carbonate, which are primarily used for adjustment of specific gravity. An antioxidant and others may also be added where appropriate.
The outside diameter of the solid core is set preferably in a range of 30-42 mm, and more preferably in a range of 32-40 mm. If it is smaller than 30 mm, the thickness of the cover becomes relatively thick, which tends to degrade resilience. If it is greater than 42 mm, the cover becomes thin, which makes molding of the golf ball difficult, and also degrades durability of the ball.
The solid core is configured such that the amount of deformation under loads from an initial load of 98 N to a final load of 1275 N falls in a range of 2.5-5.0 mm, and more preferably in a range of 2.8-4.5 mm. If it is less than 2.5 mm, hardness increases, resulting in unfavorable hit feeling. If it exceeds 5.0 mm, it becomes too soft.
In the present invention, the solid core refers not only to a simple solid core but also to a thread-wound core obtained by winding a rubber thread around a simple solid core. Further, the solid core may have either a single-layer structure or a multilayer structure made of two or more layers.
The volume of the solid core, in which the microcapsules are blended according to the present invention, with respect to the total volume of the golf ball is preferably in a range of 30-90% and more preferably in a range of 60-85%. If it is less than 30%, the effect of the present invention cannot be obtained sufficiently. If it exceeds 90%, the cover becomes relatively thin, so that durability of the golf ball is deteriorated.
Crosslinking reaction of the rubber composition of the solid core described above is conducted, e.g., at a temperature of 120-230xc2x0 C. for 10-50 minutes, preferably at 130-200xc2x0 C. for 10-40 minutes, and more preferably at 140-180xc2x0 C. for 10-40 minutes. A relation between the heating temperature (A) and the softening point (B) of the thermoplastic resin as a film material of the microcapsule is set such that (A-B) falls preferably in a range of 10-100xc2x0 C., more preferably in a range of 20-90xc2x0 C., and still more preferably in a range of 30-80xc2x0 C.
If (A-B) is less than 10xc2x0 C., release of the co-crosslinking agent and the organic sulfur compound from the microcapsules becomes slow, which lengthens the time required for crosslinking, thereby degrading productivity. If (A-B) exceeds 100xc2x0 C., the microcapsules may break during kneading of the rubber composition, in which case the effect of the present invention cannot be achieved.
Specifically, if the crosslinking reaction is expected at a temperature from 140xc2x0 C. to 170xc2x0 C., it is preferred to employ thermoplastic resin such as polystyrene or polyethylene whose softening point is approximately 100-120xc2x0 C. Since the crosslinking reaction is exothermic, the crosslinking temperature becomes higher than the temperature to which the mold is heated. Therefore, it is preferred to control the crosslinking temperature according to the actual measurement inside the solid core.
If the rubber composition of the solid core is kept at a temperature below the softening point of the thermoplastic resin, graft polymerization of the co-crosslinking agent will not occur within the rubber composition. In such a case, the necessity of adjusting the time from kneading to molding is lessened.
The softening point of the thermoplastic resin is measured using an analytical device TMA as follows. A measuring stylus under a load is rested on a sample of the thermoplastic resin in a plate form. The sample is heated at a prescribed rate of 5xc2x0 C./min, for example, and the temperature at which the measuring stylus penetrates into the sample is obtained.
The golf ball of the present invention is formed by covering the above-described solid core with a cover. As the cover composition, trans 1,4-polyisoprene, ionomer resin, polyethylene resin, polypropylene resin, polyester type thermoplastic elastomer, polyamide type thermoplastic elastomer, polyurethane type thermoplastic elastomer, polystyrene type thermoplastic elastomer or the like may be used alone or by mixing together.
Herein, the trans 1,4-polyisoprene refers to the one having a trans content of at least 60% in the polyisoprene molecule. The one having a trans content of less than 60% has a low degree of crystallinity and thus the softening point thereof is too low. It cannot satisfy the basic characteristics as a cover.
Examples of the ionomer resin include: a copolymer of xcex1-olefin and xcex1,xcex2-unsaturated carboxylic acid with a carbon number of 3-8, having at least a portion of carboxyl group therein neutralized by a metal ion; and a terpolymer of xcex1-olefin, xcex1,xcex2,-unsaturated carboxylic acid with a carbon number of 3-8 and xcex1,xcex2-unsaturated carboxylate with a carbon number of 2-22, having at least a portion of carboxyl group therein neutralized by a metal ion. As the xcex1-olefin above, ethylene, propylene, 1-butene, 1-pentene or the like may be used. Among them, ethylene is preferable in particular. As the xcex1,xcex2-unsaturated carboxylic acid with a carbon number of 3-8, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid or the like may be used. Among them, acrylic acid and methacrylic acid are particularly preferable. As the xcex1,xcex2-unsaturated carboxylate with a carbon number of 2-22, methyl ester, ethyl ester, propyl ester, n-butyl ester, isobutyl ester or the like of acrylic acid, methacrylic acid, fumaric acid, maleic acid or the like may be used. Among them, acrylate and methacrylate are particularly preferable.
For neutralization of at least a portion of the carboxyl group within the copolymer of xcex1-olefin and xcex1,xcex2-unsaturated carboxylic acid having a carbon number of 3-8 or the terpolymer of xcex1-olefin, xcex1,xcex2-unsaturated carboxylic acid having a carbon number of 3-8 and xcex1,xcex2-unsaturated carboxylate having a carbon number of 2-22 described above, sodium ion, lithium ion, zinc ion, magnesium ion, potassium ion or the like may be used.
In the cover composition of the present invention, from the standpoint of improving durability and resilience, a polymer component chiefly containing thermoplastic resin and/or thermoplastic elastomer is preferably used. In particular, the durability and the resilience will be further improved if the ionomer resin is included 50 wt. %, and more preferably 70 wt. %, within the polymer component.
The thickness of the cover is preferably in a range of 0.35-6.35 mm, more preferably in a range of 0.7-5.35 mm, and still more preferably in a range of 1.0-4.0 mm. If it is less than 0.35 mm, strength and durability of the cover are degraded. If it exceeds 6.35 mm, a volume percent of the cover composition in the entire ball becomes large, so that resilience of the ball is degraded.
In the cover described above, fiber-reinforced rubber, fiber-reinforced resin, inorganic single-crystal component, specific gravity adjusting agent, metallic powder, metal oxide, pigment, colorant, fluorescent brightening agent, lubricant, UV absorbent, photo-stabilizer, antioxidant and others may also be blended where appropriate.
The golf ball of the present invention is manufactured as follows. The cover composition is first kneaded with a roll or a kneader. To envelop the solid core with the cover composition, the cover composition may be preformed into half shells. In this case, the solid core is enveloped with two such half shells and press-molded at 130-170xc2x0 C. for 1-5 minutes. Alternatively, the cover composition may be injection-molded directly on the solid core to envelop the core.